Method for eliminating growth of weeds



United States Patent 2,997,379 METHOD FOR ELIMINATING GROWTH OF WEEDSLyle D. Goodhue, Bartlesville, Okla, assign'or to Phillips PetroleumCompany, a corporation of Delaware N0 Drawing. Filed Feb. 18, 1957, Ser.No. 640,596 '17 Claims. (Cl. 71-23) This invention relates to killing orcontrolling the growth of weeds and to compounds for doing the same. Inone of its aspects, the invention relates to a method for killing weedsemploying a compound as described below. In another aspect, theinvention relates to herbicidal composition of matter containing atleast one of said compounds as an essential active ingredient.

In a further aspect of this invention, there is provided a method forcontrolling the growth of foliage and weeds, especially in fields ofagricultural crops and areas in which grasses which are undesired thereare found by employing at the locus at which control is desired acompound as described below.

The use of chemicals to control the growth of foliage is well known inthe art. Various chemicals have been used to control weeds in fields ofagricultural crops, while others have been employed to selectively killgrasses which are growing on the same plot with other grasses. Whilemany compounds are 'known to exhibit herbicidal activity, thedevelopment of newer and more eflicient herbicides is a continuingprocess.

An object of this invention is to provide new and useful herbicides,said herbicides exhibiting a high degree of herbicidal activity. Anotherobject of the invention is to provide a method of killing or controllingundesirable weeds. Other aspects, objects, as well as the severaladvantages of the invention are apparent from this disclosure and theclaims.

According to the invention, there are used as herbicides compoundshaving the following structural characteristics:

( H H H m t lgem-ol l mwherein R is selected from the group consistingof hydrogen, an alkyl group containing from 1 to carbon atoms,inclusive, an acyl radical, halogen-substituted acyl radical containingfrom 2 to 10 carbon atoms, and R is selected from the group consistingof an aryl radical and substituted aryl radical containing from 6-10carbon atoms; the substituents on said substituted aryl radical beingselected from the group consisting of alkyl, halogen, N0 hydroxyl,alkoxy, haloalkoxy, and SO H. As disclosed herein, halogen is intendedto mean chlorine, bromine, iodine, and fluorine.

The herbicides of this invention can be used in conjunction with anysuitable carrier or solvent which does not have a harmful effect on theherbicidal activities of these compounds. These herbicides are usuallyquite eflective when applied to an area which contains the foliage to beexterminated in an amount in the range between 10 to 200 pounds peracre. The percentage of active ingredient (herbicide) in these solutionsusually 2,997,379 i atented Aug. 22, 1961 will be in the range of 0.1 to5% by weight, preferably between 0.5 and 2.0 on the same basis. Suitablesolvents or carriers include straight chain, branched chain and cyclicparaflinic hydrocarbons containing at least 5 carbon atoms such asn-pentane, cyclohexane, octane, and the like. A now particularlypreferred solvent is HF heavy alkylate, an isoparaflinic hydrocarbonhaving an approximate boiling range of 260 to 800 F. prepared byalkylation of, say, isobutane with, say, butylene in presence ofhydrofluoric acid, as described more fully in US. Patent 2,773,920, L.H. Vautrain and E. Strunk, issued December 12, 1956. This type ofisoparaflim'c carrier is available in the trade as Soltrol. Thisadjuvant carrier enhances the toxicity of the active ingredient.

A herbicide is used to kill or inhibit growth of weeds or undesirableplants. Control, as applied to controlling undesirable weeds and plantfoliage, means inhibition, but it can also mean killing of a plant orweed. Kill is defined as destroying the life of a plant or weed.Selective kill is defined as an operation used to kill growingundesirable plants in an area in which desirable plants are growingwithout killing the desirable plants.

The following specific examples are indicative of the herbicidalactivity of the herbicides of this invention.

EXAMPLE I Various substituted butenes and butanes were tested forpre-emergence herbicidal activity by the following procedure.

Six-inch clay flower pots were partly filled with soil, and six kinds ofseeds were planted in each pot. A metal divider was used to assist inplanting the seeds. The different varieties of seeds were always plantedin the same order. Beans were planted first, followed by com, radishes,rye grass, millet and cotton. The surface of the soil was then sprayedwith a solution of 0.1 gram of the chemical to be tested in 10milliliters of acetone. This corresponds to a rate of 50 pounds peracre. During the spraying, the pot was rotated on a turntable to assurean even distribution of the spray. Each of the pots was then given 250milliliters of water by means of a per.- forated one-gallon tin pail.Other waterings were given from time to time as needed, and the humiditywas kept as high as possible by water in the pans in which the pots wereset.

'After one week, the condition and number of plants in each pot wasrecorded. A scale was adopted in which 0 designates no growth, while 3indicates normal growth. At the end of the second week, the plants wereagain checked to see if any change in the observed results had takenplace. The results were then recorded, and the plants were discarded.The results of these tests are expressed below as Table I.

1 These two compounds were subsequently sprayed onto growing corn,beans, and cotton, and exhibited strong herbicidal activity.Furthermore, the herbicides exhibited hormine activity on corn, beansand cotton in that they caused a curling of the leaves of the plant.

' EXAMPLE 11 Various substituted butenes and butanes were tested asherbicides for Bermuda grass by the following procedure.

The compound to be tested was dissolved in HF heavy alkylate to form asolution containing 1 percent by weight of the active compound. Tenmilliliters of the 1% solution was then applied to healthy plugs ofBermula grass,

. 4 (a), (b) and above given by structural formula are: (a)2-phenyl-4-methoxy-l-bntene 2- 2,4-diethy1phenyl) -4-decoxy-l-butene 2-(2-hydroxyphenyl -4-tert-butoxyl-butene each growing in 4 inch clayflower pots. This corre- 2-(4-chlorophenyl)-4-isopropoxy-l-butene spondsto 100 pounds per acre. of the herbicide. The2-phenyl-4-acetoxy-l-butene plugs of grass hadbeen growing for twoweeksto one 2-(2,3-dirnethyl-6-acetoxyphenyl)-4-caproxy-1-butene month beforethey were sprayed. The sprayed plugs2-(2,4-dichlorophenyl)-1-butene-4-ol were then checked at 3 days oneweek two weeks and (b) 2 v a -phenyl-2,4-drmethoxybutane r 3 weeks.Theresults of these tests are expressed below 10 4 tert butylphenyl) 4acct? as Table II. butane I Table H Z-p-tolyl-Z-rnethoxy-4-acetoxybutanei Y 2-(S-hydroxyphenyl)-2,4-dihydroxybutane Resulismter1-2-(3-ch1oro-4-chloromethoxyphenyl)-2-hydroxy-4-de- Compound 1 coxybutane3 Days 1 Week 2 Weeks 3 Weeks 2-phenyl-2caproxy-4-chloroacetoxybutane hs 2-(Z-nitro-4-tert-butylphenyl)-2,4-didecoxybutane 2- l-1-b t +1 s M d-MG. ggg 9? $235 g g 2-phenyl-2-hydroxy-4-acetoxybutane z ghfifihiiitfifii bfitifiti-: Se i7 Sat: Mar: iiG. -P Y Y Y-2-phenyl-4-monochloroacetoxy-1- KT.-- KT KT NG2-phenyl-4-acetoxy-Z-butene butene' 2-(2-chloroacetoxyphenyl)-4-caproXy-2-butene Le end' KT-kill to Sev severe burn s1 -sli ht owth'z'uA-diethylphenyl)AmethOXYQ'bUteHe Mod. -moderate burn; ha a -moderategrowth; NG-ho gi owtfi GG 2'(3Sulf0l 7heny1)'4'tert"butoxy'zbutene goodgrowth. 2-(2,4,6-tr1chlorophenyl) -4-decoxy-2-butene EXAMPLE 12phenyl-4-(Z-chlorocaproxy)-2-butene o f the herbicides f the presentinvention, Reasonable variation and modification are possibleyl-1-butene-4-ol, was tested for herbicidal activity by the Wlthm the Pof fofegolng disclosure and t? germinating cucumber seed test. This testwas developed P k claims to the mvemlon the essence of Whlch by theCrops Division, Camp Detrick, Maryland, and i that the above-definedcompounds or compounds having reported in publication 3 4 f the NationalAcademy f the foregoing defined structural characteristics have beenSciences of the National Research Council. This test is found to beworthwhile herbicidal composition ingredients based on the inhibition fgrowth of the primary root f and that methods for using the same havebeen described. germinating cucumber seeds. In this test, 25 cucumberIcialm: seeds of the Early Fortune variety are placed on ifilterehmmatmg growth of weeds i paper in a Petri dish and 1s milliliters of avery dilute 9 aPIflYIEIg the at 18 solution of the compound to be testedin water and an effectwe arpmint h acetone is added to the dish. Thedishes are then covered memo? ehrgmatmg wfieds whlcil and incubated inthe dark for 96 hours at 28 C at 40 con-1p Uses app to t e locus at w mSue control 18 r deslred, an efiective amount of2-phenyl-4-monochlorowhich time the length of the primary roots aremeasured aoetoxy l butene in millimeters. Each test was run ntrlplicate. A check 3 A method for eliminating growth of weeds which runwas made 111 whlch I10 herblclde was PR the comprises applying to thelocus at which such control is seeds, and a comparison run was also madein wh1ch a d i d, an eifective amount of 2-phenyl-4-methoxy-1-commercial herbicide was employed. The results of these butene. runs aregiven below in Table III. 4. A method for eliminating growth of weedswhich Table lIlf Ooncen- Millimeters Root Growth Total Avg. PercentCompound tration, mm. mm. of

ppm. Root Root Normal Dish 1 Dish2 Dish3 Growth Growth Growth2-phenyl-1-butene-4-ol 0. 1 466 849 260 1, 57s 21. 00 4sZ-phenyl-l-buteneA-ol. 1. o 319 338 257 944 12. 59 292-phenyl-1-butene-4-ol 10.0 111 103 119 339 4. 52 10 Commercialherbicide 1.0 206 162 2 578 7.71 18 Control (Normal Growth)- 0 899 1,131 1,233 3, 263 43. 51

1 Commercial herbicide sold under the trade name of Esteron 10-10, andcontaining a 2,4di or 2,4,5-trichlorophenoxyacetic acid compound.

1 The solutions were made by dissolving the compound in acetone to forma 1% (by wt.) solution, and this solution was then diluted with wateruntil the desired concentration was reached.

It will be noted that selected members of the groups of herbicidesdisclosed herein can be applied to sterilize soils for certain periodsof time as is sometimes useful in the construction industry. Also,control of seeds of undesired plants can be effected by sterilizing thesoil at their best germination time with a sterilizing quantity ofcompound which will leach away by the time desired seeds are to beplanted or germinated.

comprises applying to the locus at which such control is desired, anefiective amount of 2-(2,4-diethylphenyl)-4- decoxy l butene.

5. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an efiective amount of2-(2-hydroxyphenyl)-4- tert-butoxy-l-butene.

v 6. A method for eliminating growth of weeds which Specific compoundsfalling within the several groups comprises applying to the locus atwhich such control is desired, an effective amount of2-(4chlorophenyl)-4-isopropoxy-l-butene.

7. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an effective amount of2-phenyl-4-acetoXy-1- butene.

8. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an efiective amount of2-(2,3-dimethyl-6-acetoxyphenyl) -4-caproxy-1-butene.

9. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an effective amount of2-(2,4-dichlorophenyl)-lbutene-4-ol.

10. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an effective amount of2-phenyl-4-hydroXy-2- butene.

11. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an efiective amount of2-phenyl-4-acetoxy-2- butene.

12. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an efiective amount of2-(2-chloroacetoxyphenyl) -4-caproxy-2-butene.

13. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an effective amount of2-(2,4-diethylphenyl)-4- methoxy-Z-butene.

14. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an effective amount of2-(3-sulfophenyl)-4-tertbutoxy-Z-butene.

15. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an effective amount of2-(2,4,6-trichlorophenyl)- 4-decoxy-2-butene.

16. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an effective amount of2-phenyl-4-(2chlorocaproxy)-2-butene.

17. A method for eliminating growth of weeds which comprises applying tothe locus at which such control is desired, an elfective amount of acompound selected from the group consisting of 2-phenyl-l-butene-4-ol,2-phenyl- 4-monochloroacetoxy-l-butene, 2-phenyl-4-methoXy-1-butene,2-(2,4-diethylphenyl)-4-decoxy-1-butene, 2-(2-hydroxyphenyl)-4-tert-butoxy-l -butene, 2- (4-chlorophenyl) 4-isopropoxy-l-butene,2-phenyl-4-acetoXy-1-butene, 2- (2,3-dimethyl 6acetoxyphenyl)4-caproxy-l-butene, 2- (2,4-dichlorophenyl)-l-hutene-4-ol,2-phenyl-4 hydroxy- Z-butene, 2-pheny1-4-acetoxy-2-butene,2-(2-chloroacetoxyphenyl -4-caproxy-2 -b utene, 2- 2,4-diethylphenyl)-4- methoxy-2-butene, 2- 3 -sulfophenyl) 4-tert-butoXy-2-butene,2-(2,4,6-trichlorophenyl)-4-decoXy-2-butene, and 2- phenyl-4-2-chlorocaproxy) -2-butene.

References Cited in the file of this patent UNITED STATES PATENTS2,335,384 Bousquet et al Nov. 30, 1943 2,392,859 Meuli Jan. 15, 19462,554,947 Joos May 29, 1951 2,575,282 McKay Nov. 13, 1951 2,587,566 BucFeb. 26, 1952 2,704,246 Goodhue et a1 Mar. 15, 1955 2,744,817 ToornmanMay 8, 1956 2,768,212 Copenhaver Oct. 23, 1956 2,834,747 Short et a1.May 13, 1958 2,840,598 Schwartz June 24, 1958 OTHER REFERENCES King:U.S. Dept. of Agriculture Handbook, No. 69, May 1954, page 92.

Thompson et al.: Botanical Gazette, vol. 107, pages 475-507, 1946.

1. A METHOD FOR ELIMINATING GROWTH OF WEEDS WHICH COMPRISES APPLYING TOTHE LOCUS AT WHICH SUCH CONTROL IS DESIRED, AN EFFECTIVE AMOUNT OF2-PHENYL-1-BUTENE-4-OL.